CN117457996A - Double-crosslinking composite electrolyte membrane and preparation method and application thereof - Google Patents

Double-crosslinking composite electrolyte membrane and preparation method and application thereof Download PDF

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CN117457996A
CN117457996A CN202311791808.1A CN202311791808A CN117457996A CN 117457996 A CN117457996 A CN 117457996A CN 202311791808 A CN202311791808 A CN 202311791808A CN 117457996 A CN117457996 A CN 117457996A
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spinning
electrolyte membrane
double
composite electrolyte
lithium salt
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CN117457996B (en
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周飞
周莉莎
刘强
何俊
张跃钢
黄俊杰
周胜强
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Anhui Mengwei New Energy Technology Co ltd
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Anhui Mengwei New Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • General Chemical & Material Sciences (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

The invention provides a double-crosslinking composite electrolyte membrane and a preparation method and application thereof. The preparation method comprises the steps of dissolving a high polymer in a solvent to prepare spinning solution, preparing a nanofiber skeleton through a spinning technology, mixing the high polymer with lithium salt and solid electrolyte, mixing the mixture with the nanofiber skeleton, drying, and hot-pressing to prepare the double-crosslinked composite electrolyte membrane, wherein fluid coaxial auxiliary spinning is adopted in the spinning process, and auxiliary drafting and correction are carried out on spinning jet flow, so that stable continuous preparation of the solid double-crosslinked composite electrolyte membrane with uniform diameter is realized, lithium salt and solid electrolyte particles can be uniformly dispersed in the high polymer, and the lithium salt and the high polymer are mutually crosslinked in groups to form an internal ion passage, thereby improving the stability of the electrolyte.

Description

Double-crosslinking composite electrolyte membrane and preparation method and application thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a double-crosslinking composite electrolyte membrane, and a preparation method and application thereof.
Background
With the gradual development of the energy density of the lithium ion battery to the limit level, the development of a novel battery with higher energy density is urgently needed, but the improvement of the energy density of the battery inevitably leads to the occurrence of the safety problem of the battery. In order to meet the future energy demand, all-solid-state lithium metal batteries are gradually paid attention to by vast scientific researchers, and have high energy density and high safety and stability.
In order to promote lithium ion transport between the solid electrolyte and the electrode active material, stable and firm interface contact between the electrode and the solid electrolyte membrane is required. The traditional polymer all-solid-state electrolyte has high chemical stability to air and lithium metal negative electrode due to excellent ductility at high temperature, so that the process steps of the traditional polymer all-solid-state electrolyte in the preparation process of the all-solid-state lithium metal battery are simplified, and the traditional polymer all-solid-state electrolyte is the earliest to realize commercial application. However, the polymer all-solid electrolyte has a narrow electrochemical window, is easy to decompose in a high-voltage region, has low ionic conductivity, is difficult to realize at room temperature, and can be practically applied under the condition of high temperature of 60 ℃. In order to overcome the problems, the oxide and sulfide all-solid electrolyte is used as a filler to be filled into the polymer all-solid electrolyte to prepare the all-solid electrolyte membrane, so that the high ion conductivity, the high-voltage charge-discharge stability and the long-cycle process required by the battery operation can be met, the growth of lithium dendrites can be inhibited, the complex process steps in the battery manufacturing process can be simplified, the production efficiency can be easily improved, and the production cost can be reduced. In the preparation process of the existing all-solid electrolyte membrane, oxide and sulfide all-solid electrolyte fillers are easy to agglomerate in the polymer all-solid electrolyte, so that membrane components are uneven, the prepared all-solid electrolyte membrane is low in ionic conductivity, short circuits caused by penetration of lithium dendrites are caused in the operation process of the battery due to insufficient local stress, and some safety problems are caused, so that on the premise of ensuring simple preparation process and low production cost, the oxide and sulfide all-solid electrolyte has an even dispersing effect in the polymer all-solid electrolyte, and the problems are urgent to be solved at present. And the film thickness prepared by the traditional polymer all-solid electrolyte through a tape casting molding mode is not easy to control, and excessive hot pressing can cause that the ion transfer channel of the polymer of the material and the polymer phase continuity are influenced after the polymer and the oxide sulfide are compounded, so that the mechanical and electrical properties of the material are affected. Therefore, the technology of preparing ultrathin solid electrolyte by adopting the electrostatic spinning technology becomes a research hot spot in recent years.
There are two general methods for preparing solid nanofiber electrolyte membranes, the first is to dip the prepared nanofiber/nanofiber membrane in salt solution, the method has the problem of uneven distribution in the ion permeation process and the post-treatment easily causes the change of the morphology of the fiber, so that the usability of the material is poor. Another method is to use a solution spinning method to mix and dissolve salt ions and polymers, and spin the solution by an electrostatic spinning method to obtain a solid electrolyte, however, the method has great problems as follows: the electrostatic spinning method is severely affected by the conductivity of the spinning solution, and after the conductive ions are doped in the spinning solution, the spinnability of the spinning solution is severely deteriorated, and the spinning solution is severely dithered in the spinning process, so that fiber film defects caused by splashing of the spinning solution are caused, and the current method is mostly to reduce the spinning speed, so that when the solution containing the conductive ions is prepared by using the electrostatic spinning method, the obtained fiber is poor in uniformity and low in spinning efficiency, and the practical application of the solid electrolyte is greatly limited.
Disclosure of Invention
The invention mainly aims to provide a double-crosslinking composite electrolyte membrane as well as a preparation method and application thereof, and overcomes the defects of the prior art.
In order to achieve the technical effects, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a double-crosslinking composite electrolyte membrane, which comprises the following steps: comprises dissolving high molecular polymer in solvent to obtain spinning solution, and preparing nanofiber skeleton by spinning process; and mixing the high polymer, lithium salt and solid electrolyte, and then mixing with the nanofiber skeleton to prepare the double-crosslinking composite electrolyte membrane.
Further, the method comprises the following steps:
s1, dissolving the high molecular polymer in the solvent to prepare spinning solution;
s2, spinning the spinning solution in the step S1 through a spinning process to obtain a nanofiber skeleton, wherein in the spinning process, at least a first spinning port and a second spinning port are coaxially arranged, the diameter of the first spinning port is smaller than that of the second spinning port, the first spinning port sprays out the spinning solution, and the second spinning port sprays out the fluid to draft and correct the spinning solution so as to assist spinning;
s3, mixing the high polymer with lithium salt and solid electrolyte, then mixing with the nanofiber skeleton, and drying to obtain the double-crosslinking composite electrolyte membrane.
Further, adding lithium salt into the S1 and mixing the lithium salt and the high molecular polymer in the solvent to prepare the spinning solution; further, adding a cross-linking agent to prepare the spinning solution; and (2) adding a cross-linking agent at the second spinning port in the step (S2) to carry out a spinning process.
Further, the solid electrolyte comprises any one of oxide solid electrolyte and sulfide solid electrolyte, and the main function of the oxide solid electrolyte is to further improve the ionic conductivity of the double-crosslinked composite electrolyte membrane, enhance the Young modulus of the double-crosslinked composite electrolyte, inhibit the growth of lithium dendrites and effectively improve the safety of the all-solid-state lithium metal battery in the operation process.
Further, the oxide solid electrolyte has a median particle diameter of 50 to 300 nm; the sulfide solid state electrolyte has a median particle diameter of 1-50 μm.
Further, the oxide solid state electrolyte comprises a combination of any one or more of LATP, LLZTO, LLTO; the sulfide solid state electrolyte includes Li 10 GeP 2 S 12 、Li 7 P 3 S 11 、Li 6 PS 5 X is any one or a combination of a plurality of, wherein X is Cl or Br or I.
Further, S3 comprises mixing the high molecular polymer with the lithium salt and the solid electrolyte, then mixing with the nanofiber skeleton, and drying in vacuum or argon atmosphere to obtain the double-crosslinking composite electrolyte membrane.
Further, in S3, the mass ratio of the high molecular polymer to the lithium salt is 10-1:1, mixing a high polymer and lithium salt in a solvent, adding solid electrolyte particles with the mass of 5% -50% of the high polymer, mixing with the prepared nanofiber skeleton, and drying to obtain the electrolyte membrane.
Further, S3 further includes hot pressing the double-crosslinked composite electrolyte membrane.
Further, the hot pressing condition comprises that the pressure is 0-100Mpa, the temperature is 30-80 ℃ and the time is 3-180min.
Further, the hot pressing is performed such that the thickness of the double crosslinked composite electrolyte membrane is 30 μm to 100 μm.
Further, the fluid in S2 includes any one of argon, nitrogen and lithium salt solution.
Further, the fluid pressure is 5 psi-50 psi, and the fluid movement direction is consistent with the spinning solution movement direction.
Further, the lithium salt comprises LiCl, liPF 6 、LiTFSI、LiFSI、LiClO 4 、LiBF 4 、LiAsF 6 、LiDFOB、LiBOne or more combinations of OB.
Further, the high molecular polymer comprises one or more of silk protein, chitosan, carboxymethyl fiber, hemicellulose, sodium alginate, polyamide, polymethyl methacrylate, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, polyvinylpyrrolidone and zein.
Further, the solvent comprises one or more of water, ethanol, formic acid, acetic acid, acetonitrile, methylene chloride, tetrahydrofuran, N-hexane, N-heptane, toluene, xylene, N-decane, methylformamide, hexafluoroisopropanol, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, N dimethylacetamide, fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methylethyl carbonate, 1, 3-dioxolane, 2-methyltetrahydrofuran, dimethoxymethane, 1, 2-dimethoxyethane, diethylene glycol dimethyl ether, ionic liquid.
Further, the cross-linking agent comprises one or more of epichlorohydrin, organic branched salt tetrabutylammonium chloride, copper fluoride, triphenyl phosphite, triallyl phosphate, triphenyl phosphate, amine hexafluorophosphate, boron nitride, 1,2,3, 6-tetrahydrophthalic anhydride, metal Organic Framework (MOF), covalent Organic Framework (COF), nano silver particles and nano copper particles.
Further, the solid content in the spinning solution is between 0wt% and 20wt%, and the viscosity of the spinning solution is 0.1-10 Pa.s.
Further, the conditions of the spinning process comprise a power supply voltage of 10-60 kV, a temperature of a spinning environment of 15-40 ℃, relative humidity of the spinning environment of 0-30% and a receiving distance of 5-50cm.
On the other hand, the embodiment of the invention also provides the double-crosslinked composite electrolyte membrane prepared by the preparation method.
Further, the lithium salt and the solid electrolyte in the double-crosslinking composite electrolyte membrane are dispersed in the high-molecular polymer, and the lithium salt and the high-molecular polymer are mutually crosslinked to form an internal conductive network.
Further, the thickness of the double-crosslinked composite electrolyte membrane is 30 μm to 100 μm.
On the other hand, the invention also provides a solid lithium metal battery, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte comprises the double-crosslinking composite electrolyte membrane provided by the invention.
Compared with the prior art, the invention has the beneficial effects that:
1. the double-crosslinking composite electrolyte membrane provided by the invention can crosslink the lithium salt and the high polymer mutually, and form an internal conductive network, thereby improving the electrical property.
2. According to the double-crosslinking composite electrolyte membrane provided by the invention, the lithium salt and the solid electrolyte are uniformly distributed in the high polymer, so that agglomeration is not easy, and the mechanical property of the double-crosslinking composite electrolyte membrane is effectively improved.
3. The double-crosslinking composite electrolyte membrane provided by the invention can inhibit the growth of lithium dendrites and improve the conductivity of the lithium ion battery, so that the electrochemical performance of the all-solid-state lithium metal battery is optimized, the subsequent manufacturing process is simplified, and the qualification rate of the battery is improved.
4. The double-crosslinked composite electrolyte membrane prepared by the airflow assisted spinning and hot-pressing process has the characteristics of ultra-thin, compact and high conductivity, simplifies the preparation process of the battery core of the all-solid-state lithium metal battery, and can reduce the manufacturing cost and the process difficulty.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of the electrolyte membrane produced in example 1 of the present application.
Fig. 2 is an SEM image of the nanofiber scaffold in example 1 of the present application.
Fig. 3 is a schematic view of a three-dimensional double crosslinked network structure of an electrolyte membrane in example 1 of the present application.
Fig. 4 is a structural view of an electrostatic spinning nozzle in example 1 of the present application.
Fig. 5 is a graph showing the electrical characteristics of the electrolyte membrane-assembled solid lithium metal battery in example 4 of the present application.
Fig. 6 is a schematic structural view of a solid lithium metal battery assembled by the electrolyte membrane manufactured in example 4 of the present application.
Fig. 7 is an SEM image of the nanofiber scaffold in comparative example 1 of the present application.
Fig. 8 is a graph showing the electrical characteristics of the electrolyte membrane-assembled solid lithium metal battery of comparative example 1 of the present application.
Fig. 9 is an SEM image of the electrolyte membrane produced in comparative example 2 of the present application.
Fig. 10 is an SEM image of the electrolyte membrane produced in comparative example 3 of the present application.
Detailed Description
Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
Example 1
The embodiment provides a double-crosslinking composite electrolyte membrane, which consists of fibroin, PEO, LLZTO filler, liCl and LiTFSI conductive lithium salt, wherein the LLZTO oxide solid electrolyte particle filler is self-made modified LLZTO, and the LLZTO and the LiCl and LiTFSI conductive lithium salt are uniformly dispersed in a three-dimensional network of the composite electrolyte membrane. The preparation method comprises the following steps:
preparing an electrostatic spinning solution: first, 0.5g of LiCl was dissolved in 15mL of formic acid, and the solution was stirred sufficiently to dissolve the LiCl completely, thereby obtaining a formic acid solution in which LiCl was dissolved. And adding 2g of degummed silk into the formic acid solution dissolved with LiCl, stirring for 30 minutes to obtain an ion conductor spinning solution, adding Epoxy Chloropropane (ECH) serving as a cross-linking agent into the mixed solution, and adding the mixed solution according to the volume ratio of the cross-linking agent to the mixed solution of 1:15, wherein the solid content of the obtained spinning solution is 12wt%, and the viscosity is 1.8 Pa s.
Preparing a nanofiber skeleton: the airflow assisted electrostatic spinning method is used for spinning, two spinning ports are coaxially arranged at the spinning nozzle, referring to fig. 4, in this embodiment, the electrostatic spinning nozzle structure diagram is that a first spinning port and a second spinning port are coaxially arranged, the diameter of the second spinning port is larger than that of the first spinning port, the first spinning port sprays out spinning solution, the second spinning port sprays out fluid to assist spinning, the movement direction of the fluid is the same as that of the spinning solution, and the fluid sprayed out by the second spinning port plays roles in drafting and correcting the spinning solution. The spinning process conditions are as follows: the power supply voltage is 15kV, the spinning environment temperature is kept at 20 ℃, the relative humidity is 30%, the spinning solution pouring speed is 2mL/h, the fluid sprayed out from the second spinning port is nitrogen, the air flow pressure is 30psi, the spinning solution is received by a metal roller with the surface covered with non-woven fabrics or aluminum foils, the receiving distance is 5cm, the spinning time is 30 minutes, and the nanofiber skeleton is obtained after the solvent volatilizes.
Preparation of a double-crosslinked composite electrolyte membrane: according to the mass ratio of polyethylene oxide (PEO) to LiTFSI of 5:1, mixing and dissolving the polyethylene oxide (PEO) and LiTFSI in 30mL of anhydrous acetonitrile, mixing self-made modified LLZTO (Ke-like crystal) with the particle size of 500nm into the solution, adding the solution with the addition amount of 5% of the mass of the polyethylene oxide, stirring for 8 hours at 500r/min, vacuum-treating the obtained nanofiber skeleton at 110 ℃ for 1 hour, immediately immersing the nanofiber skeleton in the mixed liquid of an argon-filled glove box (humidity <1 ppm), keeping stirring for 30 minutes at the ambient temperature, and vacuum-drying at 60 ℃ for 8 hours to obtain the electrolyte membrane. The obtained membrane was subjected to hot pressing at 80℃for 90 minutes under a pressure of 60MPa to obtain a double-crosslinked composite electrolyte membrane having a membrane thickness of 89. Mu.m.
Example 2
The embodiment provides a double-crosslinking composite electrolyte membrane, which consists of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), PEO, LATP oxide all-solid electrolyte particle filler and LiFSI conductive lithium salt, wherein the LATP oxide all-solid electrolyte particle filler is self-made modified LATP, and the LASP oxide all-solid electrolyte particle filler and the LiSSI conductive lithium salt are uniformly dispersed in a three-dimensional network of the composite electrolyte membrane.
The preparation method comprises the following steps:
preparing an electrostatic spinning solution: 2g PVDF-HFP nanoparticles were dissolved in 20 g N, N-Dimethylformamide (DMF) and 6 g acetone solvent, stirred for 2h, then 0.5g of the organic branched salt tetrabutylammonium chloride was added to the solution to increase its conductivity. After continuously stirring the mixed solution at 45 ℃ for 2 hours, a spinning solution was obtained. The obtained spinning solution has a solid content of 10wt% and a viscosity of 1.4 Pa s.
Preparing a nanofiber skeleton: the air-assisted electrostatic spinning method was used for spinning, and the electrostatic spinning nozzle was the same as in example 1, except that the first spinning port process conditions in this example were: the power supply voltage is 30kV, the spinning environment temperature is 20 ℃, the relative humidity is 30%, the spinning solution pouring speed is 1mL/h, the fluid sprayed out from the second spinning port is air, the air flow pressure is 20psi, the spinning solution is received by a metal roller with the surface covered with non-woven fabrics or aluminum foils, the receiving distance is 10cm, the spinning time is 60 minutes, and the nanofiber skeleton is obtained after the solvent volatilizes.
Preparing a double-crosslinked composite electrolyte membrane: firstly, PEO and LiWSI are mixed and dissolved in 20mL of anhydrous acetonitrile according to the mass ratio of 10:1, LATP with the mass fraction of 50wt% relative to PEO is added, after stirring for 8 hours at 500r/min, the solution is mixed with the prepared nanofiber skeleton, and then the mixture is placed in vacuum at 60 ℃ for 48 hours to remove the solvent, so that the electrolyte membrane is prepared. Carrying out hot pressing treatment on the electrolyte membrane to obtain a double-crosslinked composite electrolyte membrane, wherein hot pressing parameters are as follows: 30Mpa, temperature: the temperature is 80 ℃ and the time is 3min, and the film thickness after hot pressing is controlled at 97 mu m.
Example 3
The present example provides a double cross-linked composite electrolyte membrane composed of PAN (polyacrylonitrile), PEO, LLTO filler, liBOB and LiPF 6 The conductive lithium salt consists of LLTO oxide all-solid electrolyte particle filler which is self-made modified LLTO and is combined with LiBOB and LiPF 6 The conductive lithium salt is uniformly dispersed in the three-dimensional network of the composite electrolyte membrane.
The preparation method comprises the following steps:
preparing an electrostatic spinning solution: the PAN powder was dried in vacuo at 60 ℃ for 12h before use. Then 2.4g of PAN powder was dissolved in 20mL of N, N-Dimethylformamide (DMF) solvent, and then mechanically stirred and sonicated at Room Temperature (RT) for 1.5 and 1.0h, respectively, to obtain PAN electrospinning solution with a solid content of 8wt% and a viscosity of 1.2 Pa s.
Preparing a nanofiber skeleton: the air-assisted electrostatic spinning process was used for spinning, and the electrostatic spinning nozzle was the same as in example 1, except that in this example, the first spinning port process conditions were: the power supply voltage is 15kV, the spinning environment temperature is approximately 20+/-5 ℃, the relative humidity is 30+/-5%, the spinning solution pouring speed is 1mL/h, the auxiliary fluid sprayed out of the second spinning port is nitrogen, the air flow pressure is 20psi, the metal roller with the surface covered with non-woven fabrics or aluminum foils is used for receiving, the receiving distance is 20cm, the spinning time is 60 minutes, and the nanofiber skeleton is obtained after the solvent volatilizes.
Preparing a double-crosslinked composite electrolyte membrane: firstly, PEO and LITFSI are dissolved in anhydrous acetonitrile according to the mass ratio of 1:1, modified LLTO accounting for 20wt% relative to the mass fraction of PEO is added, after stirring for 8 hours at 500r/min, the solution is mixed with the prepared nanofiber skeleton, and then the solvent is removed after vacuum placement at 60 ℃ for 48 hours, so that the electrolyte membrane is prepared. Carrying out hot pressing treatment on the steel plate, wherein the hot pressing parameters are as follows: 20Mpa, temperature: 60 ℃ for the following time: and 3min to obtain the double-crosslinked composite electrolyte membrane, wherein the film thickness is controlled to be 46 mu m.
Example 4
The present embodiment provides a double cross-linked composite electrolyte membrane composed of hemicellulose, PEO, MOF-ZIF 67, LLZTO filler, liBOB and LiPF 6 The LLZTO oxide all-solid electrolyte particle filler is self-made modified LLZTO, and the self-made modified LLZTO and LiTFSI conductive lithium salt are uniformly dispersed in the three-dimensional network of the composite electrolyte membrane.
The preparation method comprises the following steps:
preparing an electrostatic spinning solution: first, 0.5g of LiCl was dissolved in 15mL of formic acid, and the solution was stirred sufficiently to dissolve the LiCl completely, thereby obtaining a formic acid solution in which LiCl was dissolved. Then, 2g of hemicellulose was added to the above formic acid solution in which LiCl was dissolved, and after stirring for 30 minutes, an ion conductor spinning solution was obtained, the obtained spinning solution had a solid content of 12wt% and a viscosity of 1.8 Pa ·s. And adding the MOF-ZIF 67 serving as a cross-linking agent into the mixed solution, dispersing the mixed solution in a lithium formate chloride solution according to a volume ratio of 1:20, and placing the mixed solution in a second spinning port to serve as an auxiliary fluid, wherein the solid content is 8wt% and the viscosity is 0.6 Pa.s.
Preparing a nanofiber skeleton: the spinning is performed by using a spinning solution assisted electrostatic spinning method, and an electrostatic spinning nozzle is the same as that of embodiment 1, except that in this embodiment, the process conditions of the first spinning port are as follows: the power supply voltage is 15kV, the spinning environment temperature is 20 ℃, the relative humidity is 30%, the spinning solution filling speed is 2mL/h, and the process conditions of the second spinning port are as follows: the power supply voltage is 15kV, the spinning environment temperature is kept at 20 ℃, the relative humidity is 30%, the spinning solution pouring speed is 0.5mL/h, the fluid pressure is 50psi, the spinning solution is received by a metal roller with the surface covered with non-woven fabrics or aluminum foils, the receiving distance is 30cm, the spinning time is 30 minutes, and the nanofiber skeleton is obtained after the solvent is volatilized.
Preparing a double-crosslinked composite electrolyte membrane: according to polyethylene oxide (PEO) and Li salt (LiBOB: liLiLiPF 6 =1:3wt) was dissolved in 30mL of anhydrous acetonitrile at a mass ratio of 8:1, and the self-made modified LLZTO was mixed into the above solution in an amount of 5% of PEO mass, and stirred at 500r/min for 8 h. The nanofiber scaffold obtained was vacuum-treated at 60℃for 10 hours, and immediately immersed in an argon-filled glove box (humidity<1 ppm) of the above-mentioned mixed liquid, stirred for 30 minutes, and then vacuum-dried at 60℃for 8 hours to obtain an electrolyte membrane. The membrane is subjected to hot pressing treatment for 90min at the temperature of 80 ℃ under 60MPa, and the double-crosslinked composite electrolyte membrane with the membrane thickness of 72 mu m is obtained.
Example 5
Example 5 differs from example 1 in that in example 5, epichlorohydrin (ECH) was used as a crosslinking agent and placed in the second spinning port at a volume ratio of the crosslinking agent to the mixed solution of 1:15. The remaining conditions were the same as in example 1.
Example 6
Example 6 differs from example 1 in that in example 6, formic acid was added to adjust the solid content until the solid content in the spinning solution was 0.01wt%; the viscosity of the spinning solution was 0.1 Pa s. The remaining conditions were the same as in example 1.
The electrolyte membrane produced in example 6 has a lower solid content in the spinning solution, and is less effective than example 1, but still produces a complete electrolyte membrane.
Example 7
The present embodiment provides a double-crosslinked composite electrolyte membrane comprising PAN, PEO, LLTO filler, liBOB and LiPF 6 The conductive lithium salt consists of LLTO oxide all-solid electrolyte particle filler which is self-made modified LLTO and is combined with LiBOB and LiPF 6 The conductive lithium salt is uniformly dispersed in the three-dimensional network of the composite electrolyte membrane.
The preparation method comprises the following steps:
preparing an electrostatic spinning solution: the PAN powder was dried in vacuo at 60 ℃ for 12h before use. Then, a PAN electrospinning solution having a solid content of 20wt% and a viscosity of 20 Pa.s was obtained by dissolving 4.3g of PAN polymer powder in 20mL of N, N-Dimethylformamide (DMF) solvent, followed by mechanical stirring and ultrasonic treatment at Room Temperature (RT) for 1.5 and 1.0h, respectively.
Preparing a nanofiber skeleton: the air-assisted electrostatic spinning process was used for spinning, and the electrostatic spinning nozzle was the same as in example 1, except that in this example, the first spinning port process conditions were: the power supply voltage is 60kV, the spinning environment temperature is 15 ℃, the relative humidity is 30%, the spinning solution pouring speed is 1mL/h, the auxiliary fluid sprayed out from the second spinning port is nitrogen, the air flow pressure is 20psi, the air flow is received by a metal roller with the surface covered with non-woven fabrics or aluminum foils, the receiving distance is 50cm, the spinning time is 60 minutes, and the nanofiber skeleton is obtained after the solvent volatilizes.
Preparing a double-crosslinked composite electrolyte membrane: PEO and LITFSI are firstly dissolved in 30mL of anhydrous acetonitrile according to the mass ratio of 5:1, modified LLTO accounting for 20 weight percent relative to the mass fraction of PEO is added, and the mixture is stirred for 8 hours at 500 r/min. The solution was mixed with the prepared nanofiber scaffold and then placed under vacuum at 60 ℃ for 48 hours to remove the solvent. Preparing an electrolyte membrane, and carrying out hot pressing treatment on the electrolyte membrane, wherein the hot pressing parameter is 20MPa;60 ℃;5min; the film thickness was controlled to 66. Mu.m.
Example 8
Example 8 differs from example 4 in that in example 8, the hot pressing process was a hot pressing process at a temperature of 80℃under a pressure of 100MPa for 180 minutes to obtain a double-crosslinked composite electrolyte membrane having a film thickness of 31. Mu.m.
Example 9
Example 9 differs from example 4 in that in example 9, the solid electrolyte is sulfide solid electrolyte Li 7 P 3 S 11 The remaining conditions were identical to those of example 4.
Example 10
Example 10 differs from example 4 in that in example 4 the second spinning port assist fluid was LiCl solution, the pressure of the fluid was 5psi during the assist spinning, and the remaining conditions were the same as in example 4.
Comparative example 1
Comparative example 1 was different from example 1 in that the air-assisted spinning was not used in comparative example 1, the spinning process was performed using only the first spinning port, and the remaining conditions were kept the same as in example 1.
Comparative example 2
Comparative example 2 differs from example 1 in that no autoclave treatment was performed in comparative example 2. The remaining conditions were the same as in example 1.
Referring to fig. 9, the electrolyte membrane prepared in comparative example 2 has an uneven surface and many voids.
Comparative example 3
Comparative example 3 is different from example 1 in that after the spinning solution was prepared in comparative example 3, no nanofiber scaffold was prepared, polyethylene oxide PEO and LiTFSI were dissolved in anhydrous acetonitrile, and self-made modified LLZTO (koku crystal) having a particle size of 500nm was mixed into the above solution, and after stirring for 8 hours, it was directly mixed with the spinning solution. The remaining conditions were the same as in example 1.
Referring to fig. 10, an SEM image of the electrolyte membrane prepared in comparative example 3, in which PEO voids are more and crystallization is more on the surface of the electrolyte membrane prepared in comparative example 3.
Data characterization
Referring to fig. 1, an SEM image of the double-crosslinked composite electrolyte membrane prepared in example 1 of the present invention is shown, and it can be seen that the surface of the double-crosslinked composite electrolyte membrane prepared in example 1 is flat and dense, and referring to fig. 9, an SEM image of the electrolyte membrane prepared in comparative example 2 of the present application is shown, in contrast to the electrolyte membrane prepared in comparative example 2, which is not hot pressed, has uneven surface and many voids.
Referring to fig. 2 and 7, SEM images of the nanofiber skeletons prepared in example 1 and comparative example 1 in the present application, respectively, are compared with fig. 2 and 7, in which the spinning solution in fig. 2 does not have an agglomeration phenomenon during spinning, whereas in fig. 7, the spinning solution has a remarkable agglomeration phenomenon during spinning. In the embodiment 1, the second spinning port is added, nitrogen is sprayed to assist traction and correction of the spinning solution, so that electric field interference of the spinning solution can be effectively reduced, the problem that jet flow disorder cannot normally spin when the spinning solution with high ion content is used in a traditional electrostatic spinning method is solved, the problem that jet flow disorder collection and control are difficult when the solution gas jet spinning method is simply used is solved, the aggregation phenomenon of the spinning solution in the collection process is avoided, stability of spinning jet flow and smooth running of the spinning process are facilitated, and efficient preparation of nanofiber ionic conductors is facilitated.
Referring to fig. 3, a schematic diagram of a three-dimensional dual-crosslinked network structure of an electrolyte membrane prepared in embodiment 1 of the present application is shown, in which lithium ions and solid electrolyte particles in lithium salt are uniformly dispersed in a polymer skeleton, and the lithium salt and the polymer are crosslinked with each other to form an internal conductive network, i.e. an ion transmission path, so that the performance stability of the battery is improved.
Assembled in an argon-filled glove box using CR2032 coin cell (MTI Corporation), where H 2 O and O 2 The content is less than 0.3ppm. Using the double crosslinked composite electrolyte membrane prepared in example 4 as a separator and electrolyte, lithium metal as a battery anode, and NCM811 or LFP as a battery cathode was applied to each battery. Charge/discharge measurements were performed on a LAND battery tester (marrond electronics limited) at room temperature. Referring to fig. 6, a schematic structure of an assembled solid lithium metal battery is shown with a positive electrode material under an aluminum foil, and a double-crosslinked composite electrolyte membrane between the positive electrode material and the metal lithium, the assembled battery using the double-crosslinked electrolyte membrane prepared in example 4 has a cyclic test performance such asShown in fig. 5. The cycle times are increased, and the specific capacity and coulombic efficiency of the battery are relatively stable. The battery assembled according to the same assembly method of the other embodiments has relatively stable performance, and the specific capacity and coulombic efficiency of the battery are relatively stable as the number of cycles increases.
Referring to fig. 8, which is a graph showing the electrical properties of the electrolyte membrane-assembled solid lithium metal battery prepared in comparative example 1, it can be seen that the electrolyte membrane-assembled battery prepared in comparative example 1 was unstable in performance, when spun without the assistance of a fluid. The electrolyte membranes prepared in comparative example 2 and comparative example 3 were assembled according to the same assembly method, and the battery performance exhibited unstable as the number of cycles increased.
The conductivity of the electrolyte membranes produced in examples 1 to 10 and comparative examples 1 to 3 in the present invention are shown in table 1:
table 1 comparative tables of conductive properties of electrolyte membranes obtained in examples 1 to 10 and comparative examples 1 to 3
As can be seen from table 1, in comparative example 1, compared with example 1, no fluid-assisted spinning was performed in comparative example 1, and the spinning solution was agglomerated, resulting in a great decrease in ionic conductivity; in comparative examples 2 and 3, the electrolyte membrane produced had uneven surface and many voids, greatly reducing ionic conductivity. The thickness of the double-crosslinked composite electrolyte membrane prepared in examples 1-10 is only 30-100 μm, and the double-crosslinked composite electrolyte membrane has the characteristics of ultra-thin and high conductivity.
In addition, the invention also refers to the previous examples, and tests are carried out on other raw materials, process operation and process conditions described in the specification, and ideal results are obtained.
While the invention has been described with reference to illustrative embodiments, those skilled in the art will appreciate that various other changes can be made without departing from the spirit and scope of the invention, and thus, it is intended that the invention not be limited to the specific embodiments disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (10)

1. A preparation method of a double-crosslinked composite electrolyte membrane is characterized by comprising the following steps: comprises dissolving high molecular polymer in solvent to obtain spinning solution, and preparing nanofiber skeleton by spinning process;
and mixing the high polymer, lithium salt and solid electrolyte, and then mixing with the nanofiber skeleton to prepare the double-crosslinking composite electrolyte membrane.
2. The method for producing a double-crosslinked composite electrolyte membrane according to claim 1, comprising the steps of:
s1, dissolving the high molecular polymer in the solvent to prepare the spinning solution;
s2, spinning the spinning solution in the step S1 through a spinning process to obtain the nanofiber skeleton, wherein in the spinning process, at least a first spinning port and a second spinning port are coaxially arranged, the diameter of the first spinning port is smaller than that of the second spinning port, the first spinning port sprays out the spinning solution, and the second spinning port sprays out the fluid to draft and correct the spinning solution so as to assist spinning;
s3, mixing the high molecular polymer with the lithium salt and the solid electrolyte, then mixing with the nanofiber skeleton, and drying to obtain the double-crosslinking composite electrolyte membrane.
3. The method for producing a double-crosslinked composite electrolyte membrane according to claim 2, characterized in that: the fluid comprises any one of argon, nitrogen and lithium salt solution;
and/or, adding lithium salt into the S1 and mixing the lithium salt and the high molecular polymer in the solvent to prepare the spinning solution;
and/or the fluid pressure is 5 psi-50 psi, and the fluid movement direction is the same as the spinning solution movement direction.
4. The method for producing a double-crosslinked composite electrolyte membrane according to claim 3, characterized in that: the solid electrolyte includes any one of an oxide solid electrolyte and a sulfide solid electrolyte;
and/or adding a cross-linking agent into the S1 to prepare the spinning solution;
and/or adding a cross-linking agent at the second spinning port in the step S2 for spinning.
5. The method for producing a double-crosslinked composite electrolyte membrane according to claim 4, characterized in that: the oxide solid state electrolyte comprises a combination of any one or more of LATP, LLZTO, LLTO;
and/or the sulfide solid state electrolyte includes Li 10 GeP 2 S 12 、Li 7 P 3 S 11 、Li 6 PS 5 X is any one or a combination of a plurality of, wherein X is Cl or Br or I;
and/or, S3 further comprises hot-pressing the double-crosslinked composite electrolyte membrane to enable the thickness of the double-crosslinked composite electrolyte membrane to be 10-100 mu m;
and/or S3 comprises mixing the high molecular polymer with the lithium salt and the solid electrolyte, then mixing with the nanofiber skeleton, and drying in vacuum or argon atmosphere to obtain the double-crosslinking composite electrolyte membrane.
6. The method for producing a double-crosslinked composite electrolyte membrane according to claim 4, characterized in that: the lithium salt comprises LiCl and LiPF 6 、LiTFSI、LiFSI、LiClO 4 、LiBF 4 、LiAsF 6 One or more combinations of LiDFOB, liBOB;
and/or the high molecular polymer comprises one or a combination of more of silk protein, chitosan, cellulose, sodium alginate, polyamide, polymethyl methacrylate, polyacrylonitrile, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride, polyvinylpyrrolidone and rice protein;
and/or the solvent comprises one or more of water, ethanol, formic acid, acetic acid, acetonitrile, dichloromethane, tetrahydrofuran, N-hexane, N-heptane, toluene, xylene, N-decane, methylformamide, hexafluoroisopropanol, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, N dimethylacetamide, fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methylethyl carbonate, 1, 3-dioxolane, 2-methyltetrahydrofuran, dimethoxymethane, 1, 2-dimethoxyethane, diglyme, ionic liquid;
and/or the cross-linking agent comprises one or more of epichlorohydrin, copper fluoride, triphenyl phosphite, organic branched salt tetrabutyl ammonium chloride, triallyl phosphate, triphenyl phosphate, amine hexafluorophosphate, boron nitride, 1,2,3, 6-tetrahydrophthalic anhydride, metal organic framework materials, covalent organic framework materials, nano silver particles and nano copper particles.
7. The method for producing a double-crosslinked composite electrolyte membrane according to claim 5, characterized in that: the solid content of the spinning solution is 0.01-20wt%;
and/or the viscosity of the spinning solution is 0.1-20Pa.s;
and/or the conditions of the spinning process comprise that the power supply voltage is 10-60 kV, the temperature of the spinning environment is 15-40 ℃, the relative humidity of the spinning environment is 0-30%, and the receiving distance is 5-50cm;
and/or the hot pressing conditions comprise 0-100Mpa pressure, 30-80 ℃ temperature and 3-180min time.
8. A double-crosslinked composite electrolyte membrane produced by the production method according to any one of claims 1 to 7.
9. The double-crosslinked composite electrolyte membrane according to claim 8, wherein: the lithium salt and the solid electrolyte particles in the double-crosslinked composite electrolyte membrane are uniformly dispersed in the high-molecular polymer, and the lithium salt and the high-molecular polymer are mutually crosslinked to form an internal conductive network;
and/or the thickness of the double-crosslinked composite electrolyte membrane is 30 μm to 100 μm.
10. A solid state lithium metal battery comprising a positive electrode, a negative electrode and an electrolyte, characterized in that: the electrolyte comprising the double-crosslinked composite electrolyte membrane according to claim 8 or 9.
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